CN115536857A - Zinc-organic framework material for selectively adsorbing carbon dioxide and synthesis method - Google Patents
Zinc-organic framework material for selectively adsorbing carbon dioxide and synthesis method Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000000463 material Substances 0.000 title claims abstract description 73
- 239000013384 organic framework Substances 0.000 title claims abstract description 55
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 44
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 44
- 238000001308 synthesis method Methods 0.000 title abstract description 8
- 239000013110 organic ligand Substances 0.000 claims abstract description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- 239000002184 metal Chemical class 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 235000019253 formic acid Nutrition 0.000 claims abstract description 3
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 claims description 23
- 239000011701 zinc Substances 0.000 claims description 15
- 239000012046 mixed solvent Substances 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- KXXXUIKPSVVSAW-UHFFFAOYSA-K pyranine Chemical compound [Na+].[Na+].[Na+].C1=C2C(O)=CC(S([O-])(=O)=O)=C(C=C3)C2=C2C3=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1 KXXXUIKPSVVSAW-UHFFFAOYSA-K 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 6
- MRHFNULMVZGXSQ-UHFFFAOYSA-N 4-(4-pyridin-4-ylnaphthalen-1-yl)pyridine Chemical compound C12=CC=CC=C2C(C=2C=CN=CC=2)=CC=C1C1=CC=NC=C1 MRHFNULMVZGXSQ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002904 solvent Chemical class 0.000 abstract description 4
- -1 salt zinc nitrate Chemical class 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002429 nitrogen sorption measurement Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
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- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a zinc-organic framework material for selectively adsorbing carbon dioxide and a synthesis method thereof, belonging to the technical field of metal-organic framework preparation. The zinc-organic framework material is a MOF material synthesized by adopting a solvothermal method, and is prepared by mixing and heating N, N-dimethylformamide, ethanol and other solvents, nitric acid, metal salt zinc nitrate, and organic ligands 4,4' - (pyrene-1, 3,6, 8-tetra-yl) tetraphenyl formic acid and organic ligands 1, 4-di (pyridine-4-yl) naphthalene. The MOF material prepared by the method has the advantages of high porosity and specific surface area, good stability and easiness in preparation. The MOF material has different adsorption forces on carbon dioxide and methane, so that the MOF material has good selective adsorption performance on carbon dioxide.
Description
Technical Field
The invention relates to the technical field of metal organic framework preparation, in particular to a zinc-organic framework material for selectively adsorbing carbon dioxide and a synthesis method thereof.
Background
Natural gas is increasingly gaining attention as a clean energy source, and is more economical and environmentally friendly than traditional fossil energy sources. Since the carbon dioxide present in natural gas lowers the combustion heat value, it is necessary to develop an adsorbent for removing carbon dioxide from natural gas. Energy conservation and consumption reduction are important ways to realize sustainable development, and the application of new materials plays an important role. Therefore, the development of new materials has important scientific and practical significance.
The metal organic framework material is a novel porous material formed by coordination of inorganic metal ions or metal clusters and organic ligands. The adsorbent has the characteristics of high porosity, high specific surface area, easy modification and adjustment, definite structure and the like, and can be applied to the field of adsorption separation. The existing metal organic framework material is not easy to separate carbon dioxide and methane.
In view of the above, it is desirable to design a zinc-organic framework material for selectively adsorbing carbon dioxide and a synthesis method thereof.
Disclosure of Invention
The invention aims to provide a zinc-organic framework material for selectively adsorbing carbon dioxide and a synthesis method thereof, the obtained organic framework material has the advantages of higher porosity and specific surface area, good stability and easy preparation, and the MOF material has good selective adsorption performance on carbon dioxide due to different adsorption acting forces on carbon dioxide and methane.
In order to achieve the above object, the present invention provides a zinc-organic framework material selectively adsorbing carbon dioxide, comprising an organic ligand TBAP, an organic ligand Bpn and zinc nitrate, wherein the organic ligand TBAP is 4,4',4", 4' - (pyrene-1, 3,6, 8-tetr-enyl) tetraphenoic acid, and the organic ligand Bpn is 1, 4-bis (pyridin-4-yl) naphthalene;
the molecular structural formula of the zinc-organic framework material is [ Zn ] 2 (TBAP)(Bpn)]。
Preferably, the zinc-organic framework material belongs to an orthorhombic system, the space group is Pmmmm, and the unit cell parameter is
α＝90°，β＝90°，γ＝90°。
Preferably, the zinc-organic framework material is of a layered column structure, the binuclear metal zinc and the organic ligand TBAP form a two-dimensional layered structure, and the binuclear metal zinc and the organic ligand Bpn in the two-dimensional layered structure are connected to form a three-dimensional microporous structure.
A method for synthesizing a zinc-organic framework material for selectively adsorbing carbon dioxide comprises the following steps:
s1, mixing organic ligand TBAP, organic ligand Bpn and Zn (NO) 3 ) 2 Dissolving in a mixed solvent of N, N-Dimethylformamide (DMF), ethanol (EtOH) and nitric acid to obtain a mixed solution;
and S2, carrying out solvothermal reaction on the mixed solution in the step S1 to obtain the bulk monocrystalline zinc-organic framework material.
Preferably, the molar ratio of the organic ligand TBAP to the organic ligand Bpn in the step S1 is 1:3.
preferably, the volume (mL) ratio of the used amount of the mixed solvent per millimole of the organic ligand TBAP in the step S1 is 1:60.
preferably, HNO in the mixed solvent in the step S1 3 And EtOH in a volume ratio of 1.
Preferably, the volume ratio of DMF to EtOH in the mixed solvent in step S1 is 1.
Preferably, the solvothermal reaction temperature in the step S2 is 60-90 ℃, and the reaction time is 24-96h.
Preferably, the zinc-organic framework material is used as an adsorption material for the separation of carbon dioxide and methane gas.
The invention discloses a zinc-organic framework material prepared on the basis of organic ligands 4,4' - (pyrene-1, 3,6, 8-tetra-yl) tetraphenoic acid, organic ligands 1, 4-di (pyridine-4-yl) naphthalene and a metal zinc source. Gas adsorption experiments show that the obtained zinc-organic framework material can adsorb a large amount of carbon dioxide gas, but less methane under the same conditions. Therefore, the zinc-organic framework material can be used as a gas separating agent and has a good application prospect in the field of separation and purification.
Therefore, according to the zinc-organic framework material for selectively adsorbing carbon dioxide and the synthesis method, the obtained organic framework material has the advantages of high porosity and specific surface area, good stability and easiness in preparation, and the MOF material has good selective adsorption performance on carbon dioxide due to different adsorption acting forces on carbon dioxide and methane.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a schematic structural view (along the c-axis) of a zinc-organic framework material according to the present invention;
FIG. 2 is a plot of nitrogen sorption isotherms at 77K for a zinc-organic framework material of the present invention;
FIG. 3 is a graph of the adsorption of carbon dioxide and methane at 273K for a zinc-organic framework material of the present invention;
FIG. 4 is a graph showing the adsorption of carbon dioxide and methane at 298K for the zinc-organic framework material of the present invention.
Detailed Description
The invention provides a zinc-organic framework material for selectively adsorbing carbon dioxide, which comprises an organic ligand TBAP, an organic ligand Bpn and zinc nitrate, wherein the organic ligand TBAP is 4,4' - (pyrene-1, 3,6, 8-tetra-yl) tetraphenyl formic acid, and the organic ligand Bpn is 1, 4-di (pyridin-4-yl) naphthalene; the molecular structural formula of the zinc-organic framework material is [ Zn ] 2 (TBAP)(Bpn)]. The zinc-organic framework material belongs to an orthorhombic system, the space group is Pmmmm, and the unit cell parameter is
α＝90°，β＝90°，γ＝90°。
The zinc-organic framework material is of a layered column structure, the binuclear metal zinc and the organic ligand TBAP form a two-dimensional layered structure, and the binuclear metal zinc and the organic ligand Bpn in the two-dimensional layered structure are connected to form a three-dimensional microporous structure.
A synthetic method of a zinc-organic framework material for selectively adsorbing carbon dioxide comprises the following steps:
s1, mixing organic ligand TBAP, organic ligand Bpn and Zn (NO) 3 ) 2 Dissolving in a mixed solvent of N, N-Dimethylformamide (DMF), ethanol (EtOH) and nitric acid to obtain a mixed solution; wherein the molar ratio of the organic ligand TBAP to the organic ligand Bpn is 1-1:3, the ratio of the dosage volume (mL) of the mixed solvent to the dosage of the organic ligand TBAP per millimole is 1:60, HNO in Mixed solvent 3 And EtOH in a volume ratio of 1.
And S2, carrying out solvothermal reaction on the mixed solution in the step S1 at the temperature of 60-90 ℃ for 24-96h to obtain the bulk monocrystalline zinc-organic framework material.
The zinc-organic framework material is used as an adsorbing material for separating carbon dioxide and methane gas.
The technical solution of the present invention is further illustrated by the accompanying drawings and examples.
Examples
A method for synthesizing a zinc-organic framework material for selectively adsorbing carbon dioxide comprises the following steps:
the first step is as follows: dissolving 0.01mmol of organic ligand TBAP,0.01mmol of organic ligand Bpn and 0.06mmol of zinc nitrate in 2mL of N, N-Dimethylformamide (DMF), 1mL of ethanol (EtOH) and 1mL of nitric acid to obtain a mixed solution, filling the mixed solution into a reaction bottle or a reaction kettle, and reacting for 72 hours in an oven at 80 ℃ to obtain a crystal sample of the microporous zinc MOF material.
The second step: selecting a single crystal sample with proper size and good crystallinity, collecting diffraction data by using a single crystal diffractometer under the condition of 298K, and refining by using a structure analysis software Olex2 to obtain a crystal structure. The specific structure is shown in the attached drawings of the specification.
The third step: in order to remove the solvent molecules in the material pore channels, the crystalline sample obtained above is soaked in methanol after being washed by DMF solvent, and the solvent exchange lasts for 3-6 times. The exchanged sample is degassed at 120 ℃ under vacuum for 12h to prepare the material for testing gas adsorption.
It can be seen from the table that the zinc-organic framework material belongs to the orthorhombic system, the space group is Pmmmm, and the unit cell parameter is
α＝90°，β＝90°，γ＝90°。
Wherein the crystal data are as follows:
the schematic structural diagram of the zinc-organic framework material in fig. 1 shows that: the binuclear metal zinc and the TBAP ligand form a two-dimensional layered structure, and the binuclear metal zinc in the two-dimensional layered structure is connected with the Bpn ligand to form a three-dimensional microporous structure.
The nitrogen sorption isotherm of the zinc-organic framework material in fig. 2 shows: the MOFs are microporous materials and have a high specific surface area.
The adsorption curves for carbon dioxide and methane for the zinc-organic framework materials in fig. 3 and 4 show: the MOF is more reactive to carbon dioxide than methane.
The above results indicate that the zinc-organic framework material has the performance of selective adsorption of carbon dioxide. The invention provides reference for the structure design and gas separation performance of the metal organic framework material, and has application prospect in the field of carbon dioxide selective adsorption.
Therefore, the zinc-organic framework material for selectively adsorbing carbon dioxide and the synthesis method thereof have the advantages that the obtained organic framework material has high porosity and specific surface area, good stability and easy preparation, and the MOF material has good selective adsorption performance on carbon dioxide due to different adsorption acting forces on carbon dioxide and methane.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (10)
1. A zinc-organic framework material for selectively adsorbing carbon dioxide, characterized in that:
the zinc-organic framework material comprises an organic ligand TBAP, an organic ligand Bpn and zinc nitrate, wherein the organic ligand TBAP is 4,4' - (pyrene-1, 3,6, 8-tetra-radical) tetraphenyl formic acid, and the organic ligand Bpn is 1, 4-di (pyridine-4-radical) naphthalene;
the molecular structural formula of the zinc-organic framework material is [ Zn ] 2 (TBAP)(Bpn)]。
2. The zinc-organic framework material for selective adsorption of carbon dioxide as claimed in claim 1, wherein: the zinc-organic framework material belongs to an orthorhombic system, the space group is Pmmmm, and the unit cell parameter is
α＝90°，β＝90°，γ＝90°。
3. The zinc-organic framework material for selective adsorption of carbon dioxide as claimed in claim 1, wherein: the zinc-organic framework material is of a layered column structure, the binuclear metal zinc and the organic ligand TBAP form a two-dimensional layered structure, and the binuclear metal zinc and the organic ligand Bpn in the two-dimensional layered structure are connected to form a three-dimensional microporous structure.
4. A method for synthesizing a zinc-organic framework material for selective adsorption of carbon dioxide according to any one of claims 1 to 3, characterized in that it comprises the following steps:
s1, mixing an organic ligand TBAP, an organic ligand Bpn and Zn (NO) 3 ) 2 Dissolving in a mixed solvent of N, N-Dimethylformamide (DMF), ethanol (EtOH) and nitric acid to obtain a mixed solution;
and S2, carrying out solvothermal reaction on the mixed solution in the step S1 to obtain the bulk monocrystalline zinc-organic framework material.
5. The method for synthesizing a zinc-organic framework material for selectively adsorbing carbon dioxide as claimed in claim 4, wherein: the molar ratio of the organic ligand TBAP to the organic ligand Bpn in the step S1 is 1:3.
6. the method for synthesizing a zinc-organic framework material for selectively adsorbing carbon dioxide as claimed in claim 4, wherein: the volume (mL) ratio of the used amount of the mixed solvent corresponding to each millimole of the organic ligand TBAP in the step S1 is 1:60.
7. the method for synthesizing a zinc-organic framework material for selectively adsorbing carbon dioxide as claimed in claim 4, wherein: HNO in the mixed solvent in the step S1 3 And EtOH in a volume ratio of 1.
8. The method for synthesizing a zinc-organic framework material for selectively adsorbing carbon dioxide as claimed in claim 4, wherein: the volume ratio of DMF to EtOH in the mixed solvent in the step S1 is 1.
9. The method for synthesizing a zinc-organic framework material for selectively adsorbing carbon dioxide as claimed in claim 4, wherein: in the step S2, the solvothermal reaction temperature is 60-90 ℃, and the reaction time is 24-96h.
10. The zinc-organic framework material for selective adsorption of carbon dioxide as claimed in claim 1, wherein: the zinc-organic framework material is used as an adsorption material for separating carbon dioxide and methane gas.
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| CN115490875A (en) * | 2022-09-28 | 2022-12-20 | 北京工业大学 | Zinc-based microporous metal organic framework material, preparation method and application in saccharin detection |
| CN116082657A (en) * | 2023-02-14 | 2023-05-09 | 北京工业大学 | Zinc-based metal organic framework material, preparation method thereof and ethylene separation application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115490875A (en) * | 2022-09-28 | 2022-12-20 | 北京工业大学 | Zinc-based microporous metal organic framework material, preparation method and application in saccharin detection |
| CN115490875B (en) * | 2022-09-28 | 2023-07-04 | 北京工业大学 | Zinc-based microporous metal-organic framework material, preparation method and application thereof in saccharin detection |
| CN116082657A (en) * | 2023-02-14 | 2023-05-09 | 北京工业大学 | Zinc-based metal organic framework material, preparation method thereof and ethylene separation application |
| CN116082657B (en) * | 2023-02-14 | 2024-04-05 | 北京工业大学 | Zinc-based metal organic framework material, preparation method thereof and ethylene separation application |
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